Several fluorinated aryl azides (2,6 and 2,4-difluorophenyl azide, 2,4,6-triflurorophenyl azide, and methyl 4-azido-2,3,5,6-tetrafluorobenzoate) were studied by laser flash photolysis techniques. In each case, the azides form singlet nitrenes which can be intercepted with pyridine to form ylides. This allowed determination of the rate constant for ring expansion of the singlet nitrene to the dehydroazepine and measurement of the absolute rate constants for reaction of the singlet nitrenes with typical quenchers.